1,3,5-Triazines containing at least one piperidine radical

ABSTRACT

Novel oligomer or polymer polyamine-1,3,5-triazines containing at least one polyalkylpiperidine radical, for example that of the formula ##STR1## processes for their production, their use for stabilizing organic material, and the organic material protected therewith against oxidative and light-induced degradation.

The present invention relates to novel oligomer or polymerpolyamine-1,3,5-triazines containing at least one polyalkylpiperidineradical, their manufacture, their use for stabilising organic material,and the organic material protected therewith against oxidative andlight-induced degradation.

Polymer diamine-1,3,5-triazines containing polyalkylpiperidine radicalsand their use for stabilising organic material are disclosed in GermanOffenlegunsschrift No. 2 636 144. It has been found, however, that anumber of serious difficulties arise in the manufacture of theseproducts, as insoluble by-products which are technically difficult toseparate are formed.

It has now been found that it is possible to obtain polymerpolyamine-1,3,5-triazines which have an excellent stabilising actionwithout the above mentioned difficulties.

Accordingly, the present invention relates to novelpolyamine-1,3,5-triazines of the general formula I ##STR2## wherein thesymbols which may or may not recur in the compound, and which on eachpossible recurrence can be the same or different, are defined asfollows: X is C₂ -C₆ alkylene, A is --O--, --S-- or --NR--, wherein R,which is also recurring or non-recurring and on each possible recurrencecan be the same or different, is hydrogen, C₁ -C₂₃ alkyl which can beinterrupted by oxygen, C₃ -C₁₂ cycloalkyl, C₇ -C₁₈ aralkyl, C₆ -C₁₀ arylor the radical of the formula II ##STR3## wherein R³ is hydrogen, C₁-C₁₈ alkyl, C₃ -C₁₂ alkenyl, C₃ -C₅ alkynyl, C₃ -C₁₈ alkoxyalkyl, C₂ -C₄hydroxyalkyl which is unsubstituted or substituted by phenyl or phenoxy,or C₇ -C₁₈ aralkyl, and R⁴ is hydrogen or methyl, or R is also one ormore of the structural units contained with the brackets of formula I,said structural unit or units being terminally saturated by U and beingbound through a triazine C-atom, and wherein R and R¹ as end groups,each independently of the other, can be hydrogen, C₁ -C₂₃ alkyl whichcan be interrupted by oxygen, C₃ -C₁₂ cycloalkyl, C₇ -C₁₈ aralkyl, C₆-C₁₀ aryl or the radical of the formula II, and R¹ as end group can alsoin addition be a group of the formula III ##STR4## wherein R⁵ and R⁶,each independently of the other, are U, C₁ -C₂₃ alkyl which can beinterrupted by oxygen, C₃ -C₁₂ cycloalkyl, C₇ -C₁₈ aralkyl, C₆ -C₁₀ arylor a radical of the formula II, and p is 0, 1, 2 or 3; m is 0, 1, 2, 3or 4, R¹ can be hydrogen, C₁ -C₂₃ alkyl which can be interrupted byoxygen, C₃ -C₁₂ cycloalkyl, C₇ -C₁₈ aralkyl, C₆ -C₁₀ aryl, the radicalof the formula II or a group of the formula IV, ##STR5## R² is halogencyano, azido, hydrazido, phenyl, --OR⁷, --SR⁷ or --NR⁸ R^(8'), whereinR⁷ is hydrogen, C₁ -C₁₈ alkyl, C₃ -C₁₂ alkenyl, C₃ -C₁₈ alkoxyalkyl, C₃-C₁₂ cycloalkyl, C₇ -C₁₈ aralkyl, C₆ -C₁₀ aryl, or the radical of theformula II, and R⁸ and R^(8'), each independently of the other, arehydrogen, C₁ -C₂₃ alkyl which can be interrupted by oxygen, C₃ -C₁₈alkenyl, C₃ -C₅ alkynyl, C₂ -C₁₀ hydroxyalkyl, C₂ -C₅ cyanoalkyl, C₃-C₁₂ cycloalkyl, C₇ -C₁₈ aralkyl, C₆ -C₁₀ aryl or the radical of theformula II, or R⁸ and R^(8') together with the nitrogen atom to whichthey are attached form a pyrrolidine ring or a piperidine, morpholine,or hexamethyleneimine ring which is unsubstituted or substituted by C₁-C₄ alkyl, or R² on each of its possible recurrences can also be aradical of the formula V ##STR6## wherein a can be 0, 1, 2, 3 or 4, or aradical of the formula VI ##STR7## wherein q can be 0, 1 or 2, and r canbe 0, 1, 2 or 3, whilst the sum of r+q may not be more than 3, or R² canalso be one or more of the structural units contained with the bracketsof formula I, said structural unit or units being terminally saturatedby Q and being bound through the amine nitrogen atom, and wherein R² asend group is halogen, phenyl, --OR⁷, --SR⁷, --NR⁸ R^(8'), a group of theformula VII, ##STR8## or of the formula VIII ##STR9## wherein A¹ is--O--, --S-- or --NR⁵, whilst Q is halogen, --NR⁸ R^(8'), --OH, --OMe/b,wherein Me/b represents an alkali metal or alkaline earth metal of thevalency b, and b is 1 or 2, or Q is a radical of the formula VII orVIII, U is hydrogen, a group of the formula ##STR10## or C₁ -C₂₄ acyl,and n can be an integer from 1 to 100, with the priviso that at leastone R, one R¹ or one R² is or contains a group of the formula II and, ifm is 0, at least one R¹ must be a group of the formula III or IV.

C₁ -C₁₈ Alkyl can be methyl, ethyl, n-propyl, isopropyl, n-butyl,sec-butyl, n-pentyl, n-hexyl, n-octyl, 1,1,3,3-tetramethylbutyl,n-nonyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl. Preferredalkyl groups are those containing 1 to 8 carbon atoms, especially thosecontaining 1 to 4 carbon atoms.

C₁ -C₂₃ Alkyl radicals are the same as those defined above for C₁ -C₁₈alkyl and are additionally e.g. nonadecyl, eicosyl, heneicosyl, docosyland tricosyl. These hydrocarbon radicals can always be straight-chain orbranched.

C₁ -C₄ Alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.butyland tert-butyl.

C₃ -C₁₂ Cycloalkyl is for example cyclopropyl, cyclopentyl, cyclohexyl,cycloheptyl, cyclooctyl, cyclononyl or cyclododecyl. Cyclohexyl ispreferred.

C₇ -C₁₈ Aralkyl is in particular 1-phenethyl, 1,1-dimethylbenzyl,2-phenylethyl or, most preferably, benzyl.

C₆ -C₁₀ Aryl is for example phenyl which is substituted by methyl,ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.Unsubstituted phenyl groups are preferred.

C₃ -C₁₈ Alkenyl is in particular C₃ -C₁₂ alkenyl, for example allyl,methyallyl, 2-butenyl, 2-hexenyl, 3-hexenyl, 2-octenyl, or 2-dodecenyl.Allyl is preferred.

C₃ -C₅ Alkynyl is for example propargyl, 1-butynyl, 2-butynyl orn-1-pentynyl. Propargyl is preferred.

The alkyl moiety of C₃ -C₁₈ alkoxyalkyl can contain 1 to 3 carbon atomsand the alkoxy moiety can contain 1 to 16 carbon atoms. Examples of C₃-C₁₈ alkoxyalkyl are: ethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl,2-n-butoxyethyl, 3-n-butoxyethyl, 2-octoxyethyl or 2-hexadecyloxyethyl.Alkoxyalkyl groups containing 3 or 4 carbon atoms are preferred, forexample ethoxymethyl, 2-methoxyethyl or 2-ethoxyethyl.

C₂ -C₁₀ Hydroxyalkyl is in particular C₂ -C₄ hydroxyalkyl, e.g.2-hydroxy-n-butyl, 2-hydroxy-n-propyl, and, in particular,2-hydroxyethyl.

Halogen is e.g. fluorine or, in particular, chlorine. R⁷ and R⁸ as C₂-C₅ cyanoalkyl are in particular cyanoethyl.

X as C₂ -C₆ alkylene is e.g. ethylene, propylene, tetramethylene,pentamethylene and hexamethylene. Ethylene and propylene are preferred.

Me as alkali metal or alkaline earth metal is in particular Na, K, Li,Mg, Ca, Sr or Ba. Na, K and Ca are preferred.

U as C₁ -C₂₄ acyl is preferably C₂ -C₈ acyl and especially acetyl,propionyl, butyryl or benzoyl. U can also advantageously be formyl.

Particularly interesting compounds are those of the formula I, wherein Xrepresents ethylene or propylene and A is --NR--, wherein R as recurringor non-recurring symbol, which can be the same or different on eachpossible recurrence, is hydrogen, C₁ -C₈ alkyl, cyclohexyl, benzyl, theradical of the formula II, wherein R³ is hydrogen, C₁ -C₁₈ alkyl, allyl,C₂ -C₄ hydroxyalkyl, benzyl, and R⁴ is hydrogen, or R is one or more ofthe structural units contained within the bracket of formula I, saidstructural unit or units being terminally saturated by U and being boundthrough a triazine C-atom, wherein R and R¹ as end groups, eachindependently of the other, can be hydrogen, C₁ -C₈ alkyl, cyclohexyl,benzyl or the radical of the formula II as defined above, and R¹ as endgroup can also in addition be a group of the formula III, wherein R⁵ andR⁶, each independently of the other, can be U or the radical of theformula II as defined above, and p can be 0 or 1; R¹ as recurring ornon-recurring symbol, which can be the same or different on eachpossible recurrence, is hydrogen or the radical of the formula II asdefined above or a group of the formula IV, wherein A, X, R and p havethe given meanings; m as recurring or non-recurring symbol, which can bethe same or different on each possible recurrence, is 0, 1 or 2; R² asrecurring or non-recurring symbol, which can be the same, or differenton each possible recurrence, is chlorine, or --NR⁸ R^(8'), wherein R⁷and R⁸, each independently of the other, are hydrogen, C₁ -C₈ alkyl,allyl, C₃ -C₄ alkoxyalkyl, C₂ -C₄ hydroxyalkyl, cyclohexyl, benzyl orthe radical of the formula II, wherein R³ is hydrogen, C₁ -C₈ alkyl,allyl, C₂ -C₄ hydroxyalkyl, benzyl, and R⁴ is hydrogen, or R² is also aradical of the formula V or VI, wherein A, X, R and R¹ have the givenmeanings, a is 1 or 2, q can be 0 and r can be 0 or 1, or R² can also beone or more of the structural units contained with the brackets offormula I, said structural unit or units being terminally saturated by Qand being bound through the amine nitrogen atom, and wherein R² as endgroup is chlorine or the group --NR⁸ R^(8') as defined above or a groupof the formula VII or VIII, wherein A' is --NR⁵ -- and X, R⁵, m and qhave the given meanings Q; is chlorine, the group --NR⁷ R⁸ as definedabove, --OH, --OMe/b, wherein Me/b is an alkali metal or alkaline earthmetal of the valency b, and b is 1 or 2, or Q is a radical of theformula VII and VIII as defined above; U is hydrogen, a group of theformula ##STR11## or acetyl, propionyl or benzoyl; and n can be aninteger from 1 to 50, with the proviso that at least one R, one R¹ orone R² is and/or contains a group of the formula II, and, if m is 0, atleast one R¹ must be a group of the formula III or IV.

Preferred compounds are those of the formula IX ##STR12## wherein m asrecurring or non-recurring symbol, which can be the same or different oneach possible recurrence, is 0, 1 or 2, R is recurring or non-recurringsymbol, which can be the same or different on each possible recurrence,is hydrogen or one or more of the structural units contained within thebracket of formula I, said structural unit or units being terminallysaturated by U and being bound through a triazine C-atom, and wherein Ras end group is hydrogen and each R¹ as end group can independently behydrogen, a group of the formula X ##STR13## and R¹ as end group canalso in addition be a group of the formula XI ##STR14## wherein R⁵ ishydrogen and R⁶ is a group of the formula X and p is 0 or 1, R¹ asrecurring or non-recurring symbol, which can be the same or different oneach possible recurrence, is hydrogen, a group of the formula X and, ifm is 0, at least one R¹ is a group of the formula XII ##STR15## whereinR and p have the given meanings, R² as recurring or non-recurringsymbol, which can be the same or different on each possible recurrence,is chlorine or --NR⁸ R^(8'), wherein R⁸ and R^(8'), each independentlyof the other, are hydrogen, C₁ -C₈ alkyl, allyl, methoxyethyl,methoxypropyl, C₂ -C₄ hydroxyalkyl, cyclohexyl, benzyl, or a group ofthe formula X; Q is chlorine, the group --NR⁸ R^(8') as defined above,--OH, --OMe/b, wherein Me/b is an alkali metal or alkaline earth metalof the valency b and b is 1 or 2; U has the preferred meaning givenabove, and n can be an integer from 1 to 50, with the proviso that atleast one R, one R¹ or one R² is and/or contains a group of the formulaX.

Particularly preferred compounds are those of the formula IX, wherein R²is a group --NR⁸ R^(8'), in which R⁸ is hydrogen and R^(8') is C₁ -C₈alkyl, cyclohexyl or a group of the formula X.

A further embodiment of the invention concerns a process for theproduction of the novel polymer polyamine-1,3,5-triazines. Thesecompounds can be obtained by methods analogous to known ones by reactinga halogeno-1,3,5-triazine of the formula ##STR16## wherein R^(2') ishalogen, cyano, azido, hydrazido. phenyl, --O--R⁷, --SR⁷ or --NR⁸R^(8'), in which R⁷ is hydrogen, C₁ -C¹⁸ alkyl, C₃ -C₁₂ alkenyl, C₃ -C₁₈alkoxyalkyl, C₃ -C₁₂ cycloalkyl, C₇ -C₁₈ aralkyl, C₆ -C₁₀ aryl or theradical of the formula II ##STR17## wherein R³ is hydrogen, C₁ -C₁₈alkyl, C₃ -C₁₂ alkenyl, C₃ -C₅ alkynyl, C₃ -C₁₈ alkoxyalkyl, C₂ -C₄hydroxyalkyl which is unsubstituted or substituted by phenyl orphoenoxy, or is C₇ -C₁₈ aralkyl, and R⁴ is hydrogen or methyl, and eachof R⁸ and R^(8') independently is hydrogen, C₁ -C₂₃ alkyl which can beinterrupted by oxygen, C₃ -C₁₈ alkenyl, C₃ -C₅ alkynyl, C₂ -C₁₀hydroxyalkyl, C₂ -C₅ cyanoalkyl, C₃ -C₁₂ cycloalkyl, C₇ -C₁₈ aralkyl, C₆-C₁₀ aryl or the radical of the formula II, or R⁸ and R^(8') togetherwith the nitrogen atom to which they are attached form a pyrrolidinering or a piperidine, morpholine, or hexamethyleneimine ring which isunsubstituted or substituted by C₁ -C₄ alkyl, with a polyamine or amixture of polyamines of the formula ##STR18## wherein X is C₂ -C₆alkylene, A is --0--, --S-- or --NR--, each R independently is hydrogen,C₁ -C₂₃ alkyl which can be interrupted by oxygen, C₃ -C₁₂ cycloalkyl, C₇-C₁₈ aralkyl, C₆ -C₁₀ aryl or the radical of the formula II, and c canbe an integer from 1 to 4, with the proviso that at least one of R^(2')or R is or contains a group of the formula II, and, if desired, treatingthe compound so obtained with an acylating agent, such that, if amixture of polyamines of the formula XIX is used, said mixture cancontain an amount of an amine of the formula XIX in which c is 0, andwhenever R^(2") is halogen, of if terminal halogen atoms are stillpresent, the compound obtained can subsequently additionally be reactedwith compounds of the formula XX

    H--R.sup.2"                                                (XX)

wherein R^(2") has the same meaning as R^(2') excepting halogen andphenyl.

The above compounds defined under formula I are products of thisprocess. Halogen is preferably chlorine.

If the product is acylated after completion of the reaction, theacylation is carried out by methods which are known per se. Suitableacylating agents are carboxylic acids containing 1 to 24, preferably 2to 8, carbon atoms, or halides or anhydrides thereof, e.g. acetic acid,acetyl chloride, acetic anhydride, propionic anhydride, butyryl chlorideor benzoyl chloride.

A preferred embodiment of the process comprises reacting cyanuricchloride with a polyamine or a mixture of polyamines of the formula XIX,wherein X, A and R are as defined above and c can be 1 or 2, such that,if a mixture of polyamines is used, said mixture can contain an amountof an amine of the formula XIX in which c is 0, and subsequentlyreacting the product obtained with compounds of the formula XX, whereinR^(2") is --OR⁷, --SR⁷ or --NR⁸ R^(8'), and R⁷, R⁸ and R^(8') are asdefined above, and, if desired, thereafter acylating the reactionproduct with an acylating agent, with the proviso that at least one ofR^(2") or R is or contains a group of the formula II as defined above.The subsequent acylation constitutes a preferred embodiment.

A particularly preferred embodiment of the process comprises the use ofa homogeneous polyamine of the formula XIX, wherein c can be 1 or 2.

If there is used a mixture of polyamines of the formula XIX containingan amount of an amine of the formula XIX in which c is 0, then saidamount preferably does not exceed 50% by weight of the mixture ofpolyamines.

Halogeno-1,3,5-triazines of the formula XVIII, wherein R^(2') is asdefined above with the exception of halogen and phenyl, can be obtainedby reacting a cyanuric halide, preferably cyanuric chloride, with 1 moleof a compound of the formula XX. Halogeno-1,3,5-triazines of the formulaXVIII, wherein R^(2') is phenyl, can be produced by methods analogous tothe procedure described in Example 14.

The reaction of the halotriazines with the compounds of the formula XIXor with the compounds of the formula XX is carried out either in aqueoussuspension or in the presence of an inert solvent, such as acetone,dioxane, toluene, or xylene, in a temperature range between -10° C. andthe boiling temperature of the solvent. The reaction takes place in thepresence of organic or inorganic bases in order to bind the hydrogenhalide. Examples of preferred bases are triethylamine or tributylamine,sodium hydroxide, sodium carbonate or sodium bicarbonate, potassiumhydroxide or potassium carbonate or calcium carbonate.

Polyamines of the formula XIX, wherein at least one R is a group of theformula II are obtained by methods which are known per se by reacting apolyamine of the formula XXI ##STR19## wherein X has the above meaningand c can be an integer from 1 to 4, with a ketone of the formula XXII##STR20## wherein R³ and R⁴ are as defined above, by means of catalytichydrogenation.

The polyamines of the formula XIX, wherein c can be an integer from 1 to4 and at least one R is a group of the formula II, and otherwise all thesymbols have the general and preferred meanings assigned to them at theoutset, are novel and can be used as intermediates and also asstabilisers in the same way as the end product of the formula I. Theycan also be used as hardeners for epoxy resins in the same way as theend products of the formula I.

The molar ratio of compounds of the formula XXI to compounds of theformula XXII can vary from 1:1 to 1:5, preferably from 1:1 to 1:2.

The molar ratio of cyanuric halides or of halotriazines of the formulaXVIII to polyamines of the formula XIX depends on the ratio of thereactive groups.

A preferred embodiment is the two-step reaction of cyanuric chloridewith a polyamine of the formula XIX, wherein at least one R is a groupof the formula II, in the ratio of 0.8-1.2:1.2-0.8, whilst retaining achlorine atom at the triazine ring, and the subsequent reaction with anexcess of an amine of the formula HNR⁸ R^(8').

The starting compounds are generally known and can be obtained bymethods which are known per se.

The polymer triazines of the present invention can be used according tothe present invention for stabilising plastics against damage by theaction of oxygen, heat and light. Examples of such plastics are thepolymers listed on pages 12 to 14 of German Offenlegungsschrift No.2,456,864.

A particularly important utility is the stabilising of polyolefins,styrene polymers and polyurethanes, for which the compounds of theinvention are exceptionally suitable.

Examples of such materials which can be stabilised by the compounds ofthe formula I are polyethylene of high and lower density, polypropylene,especially also in the form of filaments, ribbons and sheets,ethylene/propylene copolymers, polystyrene,styrene/butadiene/acrylonitrile copolymers, mixtures of polyolefins orof styrene polymers, polyurethanes based on polyethers or polyesters inthe form of films, filaments, lacquers, elastomers or foams. Thecompounds of the formula I are particularly suitable for stabilisingABS.

The stabilisers are added to the plastics in a concentration of 0.01 to5% by weight, based on the weight of the material to be stabilised.Preferably, 0.03 to 1.5, most preferably 0.2 to 0.6% by weight of thecompounds, based on the weight of the material to be stabilised, areincorporated therein.

The incorporation can be effected after the polymerisation, for exampleby blending the compounds and, if desired, further additives, into themelt by the methods conventionally employed in the art, before or duringforming, or also by applying the dissolved or dispersed compounds to thepolymers, if desired with subsequent evaporation of the solvent.

The novel compounds can also be added to the plastics to be stabilisedin the form of a master batch which contains the compounds, for examplein a concentration of 2.5 to 25% by weight. In the case of crosslinkedpolyethylene, the compounds are added before the crosslinking.

Accordingly, the invention also relates to the plastics stabilised bythe addition of 0.01 to 5% by weight of a compound of the formula I andwhich can, if desired, also contain other known and conventionaladditives. The stabilised plastics can be used in a very wide variety offorms, for example as sheets, filaments, ribbons, profiles or as bindersfor lacquers, adhesives or cements.

Examples of further additives with which the stabilisers of theinvention can be used, are: antioxidants, such as 2,6-dialkylphenols,derivatives of alkylated hydroquinones, hydroxylated thiodiphenylethers, alkylidene bisphenols, O-, N- and S-benzyl compounds,hydroxybenzylated malonates, hydroxybenzyl aromatics, s-triazinecompounds, amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionicacid, esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid,esters of β-(5-tert-butyl-4-hydroxyphenylacetic acid, acylaminophenols,benzylphosphonates, aminoaryl derivatives, UV absorbers and lightstabilisers, such as 2-(2'-hydroxypheny)-benztriazoles,2,4-bis-(2'-hydroxyphenyl)-6-alkyl-s-triazines, 2-hydroxybenzophenones,1,3-bis-2-(2'-hydroxybenzoly)-benzenes, esters of substituted orunsubstituted benzoic acids, acrylates, nickel compounds, stericallyhindered amines, oxalic acid diamides, metal deactivators, phosphites,compounds which decompose peroxide, polyamide stabilisers, basicco-stabilisers, PVC stabilisers, nucleination agents or other additives,for example plasticisers, lubricants, emulsifiers, fillers, carbonblack, asbestos, kaolin, talc, glass fibres, pigments, fluorescentwhitening agents, flame retardants, antistatic agents.

Examples of further additives with which the stabilisers of the presentinvention can be used are listed on pages 18-24 of GermanOffenlegungsschrift No. 2,427,853.

The following Examples describe in more detail the manufacture and useof the compounds of the present invention.

EXAMPLE 1

100 g of triacetone amine and 36.5 g of diethylene triamine aredissolved in 1.4 liters of methanol. To this solution are added 1.5 g ofconc. sulfuric acid and the reaction mixture is hydrogenated undernormal pressure at 20° C. to 25° C. in the presence of 5 g of 5%platinum on carbon. The uptake of hydrogen is complete after 4 hours(15.4 liters; 0° C.; 760 mm Hg).

The catalyst is filtered off, the solvent evaporated and the residuedistilled in a high vacuum. Boiling point: 161° C./0.08 mm Hg. Yield: 92g of 1,7-bis-(2,2,6,6-tetramethyl-4-piperidyl)-1,4,7-triazaheptane inthe form of a slightly yellow liquid.

19 g of 1,7-bis-(2,2,6,6-tetramethyl-4-piperidyl)-1,4,7-triazaheptaneare dissolved in 200 ml of toluene. With stirring, a solution of 9.2 gof cyanuric chloride in 50 ml of toluene is added to the above solution,followed by the addition of 6.6 g of finely powdered sodium hydroxide.The mixture is stirred for 1 hour at 0° to 5° C. and for 1 hour at 40°C. and then refluxed for 16 hours. After cooling, the insolubleconstituents are filtered off and the toluene solution is concentrated.The residue (16 g) is separated into two portions by crystallisationfrom 200 ml of hexane, affording crystals with a melting point of >260°C. and an average molecular weight M_(n) of 8100. The mother liquor isevaporated. Melting point: >260° C., M_(n) : 2640.

EXAMPLE 2

The procedure of Example 1 is repeated, except that cyanuric chloride isreacted with1,7-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,4,7-triazaheptane indifferent molar ratios:

    __________________________________________________________________________    Molar ratio of                                                                cyanuric chloride/ Melting  Analysis (%)                                      amine       Working up                                                                           point in °C.                                                                 --M.sub.n                                                                        C  H  N  O Cl                                     __________________________________________________________________________    a 1:3       crystallisation                                                                      30-40°                                                                        940                                                                             66.0                                                                             11.3                                                                             19.9                                                                             3.1                                                                             <0.1                                               from acetone                                                                  at -78° C.                                                 b 1:2*      crystallisation                                                                      100-108°                                                                     2120                                                                             63.7                                                                             10.5                                                                             20.6                                                                             4.3                                                                              0.8                                               from hexane                                                                   at -78° C.                                                 c 1:1.5     2 fractions by                                                                       260   3970                                                                             62.8                                                                             10.0                                                                             21.9                                                                             3.1                                                                              2.3                                               crystallisation                                                               from hexane                                                                   crystals from                                                                        138-186°                                                                     2250                                                                             63.5                                                                             10.4                                                                             21.5                                                                             2.3                                                                              2.2                                               mother liquor                                                     d 1:0.75    crystallisation                                                                      260   7800                                                                             59.6                                                                              8.4                                                                             22.9                                                                             1.3                                                                              7.3                                               from acetone                                                      e 1:4       crude product                                                                        resin                                                      __________________________________________________________________________     ##STR21##                                                                     ##STR22##                                                                

EXAMPLE 3

In analogy to the procedure of Example 1, 310 g of triacetone amine and160 g of triethylenetetramine in 3 liters of methanol are hydrogenatedin the presence of 2.5 g of conc. sulfuric acid and 15 g of 5% platinumon carbon. The resultant1,10-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,4,7,10-tetraazadecane boilsat 182° C./0.01 mm Hg. 21.7 g of1,10-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,4,7-tetraazadecane aredissolved in 200 ml of toluene. With stirring, a solution of 9.1 g of2-methylamino-4,6-dichlorotriazine in 100 ml of toluene is added to theabove solution at 0° C. After addition of 4.5 g of finely powderedsodium hydroxide, the mixture is stirred at 0° to 5° C. for 1 hour, thenfor 1 hour at about 20° C., and finally for 16 hours under reflux. Theinsoluble constituents are filtered off, the filtrate is concentratedand the residue is crystallised from 200 ml of cyclohexane. Meltingpoint: 130°-170° C., M_(n) : 2700.

EXAMPLE 4

The following dichlorotriazines are reacted with1,7-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,4,7-triazaheptane in themolar ratio of 1:1 in a manner analogous to that described in Example 3.

    ______________________________________                                        Dichlorotriazine derivatives employed                                          ##STR23##                                                                                                 Melting                                                             Working   point                                            R.sup.2'           up        (°C.)                                                                           --M.sub.n                               ______________________________________                                        a   OCH.sub.3          crystall- 142-163                                                                              1640                                                         isation                                                                       from                                                                          hexane                                                 b   NH.sub.2           crystall- 163-169                                                                              2140                                                         isation                                                                       from cyclo-                                                                   hexane                                                 c   NH(CH.sub.2).sub.3 OCH.sub.3                                                                     crude     69-83  1580                                                         product                                                d   NHC(CH.sub.3).sub.2 CH.sub.2 C(CH.sub.3).sub.3                                                   crude     108-116                                                                              1530                                                         product                                                     ##STR24##         crude product                                                                           125-136                                                                              2280                                  f                                                                                  ##STR25##          crude  product                                                                         130-154                                                                              1760                                  g   N(CH.sub.3).sub.2  crude     73-86  1240                                                         product                                                h   N(C.sub.4 H.sub.9).sub.2                                                                         crude     resin  1110                                                         product                                                i                                                                                  ##STR26##         crude product                                                                           resin  3010                                  ______________________________________                                    

To saturate any terminal chlorine atoms still present, the products canbe reacted with an excess of butylamine.

EXAMPLE 5

The 1,10-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,4,7,10-tetraazadecaneobtained in Example 3 is used as starting material.

25.6 g of1,10-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,4,7,10-tetraazadecane aredissolved in 200 ml of toluene. A solution of 5.5 g of cyanuric chloridein 50 ml of toluene is then added at 0° C. to the above solution inportions. Then 4 g of finely powdered sodium hydroxide are added. Themixture is stirred for 1 hour at 0° to 5° C., then for 1 hour at 40° C.and finally for 16 hours under reflux. The insoluble constituents arefiltered off and the solution is concentrated. The residue is taken upin hexane, filtered once more and the product is precipitated by coolingwith dry ice. Melting point: 100° to 120° C., M_(n) : 2240.

EXAMPLE 6

Dichlorotriazine derivatives are reacted with1,10-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,4,7,10-tetraazadecane in themolar ratio 1:1 as described in Example 3. The crude products are eitherrecrystallised or taken up in a solvent, filtered again andconcentrated.

    ______________________________________                                        Dichlorotriazine derivatives employed                                          ##STR27##                                                                                                  Melting                                                                       point                                           R.sup.2'          Working up  (°C.)                                                                          --M.sub.n                               ______________________________________                                        a   OCH.sub.3         crystallisation                                                                          53-75  1700                                                        from hexane                                             b   NH.sub.2          dissolve in                                                                              142-151                                                                              2670                                                        methylene                                                                     chloride,                                                                     filter,                                                 c   NHC(CH.sub.3).sub.2 CH.sub.2 C(CH.sub.3).sub.3                                                  dissolve in                                                                              103-118                                                                              1530                                                        hexane etc.                                             d   NH(CH.sub.2).sub.3 OCH.sub.3                                                                    dissolve in                                                                              76-94  1820                                                        hexane etc.                                                  ##STR28##        dissolve in methylene chloride etc.                                                       88-112                                                                              2050                                  f                                                                                  ##STR29##        dissolve in methylene chloride etc.                                                      128-143                                                                              1750                                  g   N(CH.sub.3).sub.2 dissolve in                                                                              110-135                                                                              1660                                                        hexane etc.                                             h   N(C.sub.4 H.sub.9).sub.2                                                                        dissolve in                                                                              65-76  1700                                                        hexane etc.                                             ______________________________________                                    

EXAMPLE 7

A mixture of 155 g of triacetone amine, 113 g of diethylene triamine,and 2.5 g of conc. sulfuric acid in 2.5 liters of methanol ishydrogenated in the presence of 7 g of 5% palladium on carbon in themanner described in Example 1. In addition to yielding1,7-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,4,7-triazaheptane,distillation of the hydrogenation mixture yields at 115°-118° C./0.09 mmHg 1-(2,2,6,6-tetramethyl-4-piperidyl)-1,4,7-triazaheptane as mainproduct.

(a) 13.9 g of2-(1,1,3,3-tetramethyl-1-butylamino)-4,6-dichloro-1,3,5-triazine arereacted with 12.1 g of1-(2,2,6,6-tetramethyl-4-piperidyl)-1,4,7-triazaheptane in the presenceof 5.4 g of powdered sodium hydroxide in the manner described inExample 1. The product is crystallised from hexane. Melting point:156°-164° C., M_(n) : 2020.

(b) 16.7 g of 2-(1,1,3,3-tetramethyl-1-butylamino)-4,6-dichlorotriazineare reacted with 9.7 g of1-(2,2,6,6-tetramethyl-4-piperidyl)-1,4,7-triazaheptane (molar ratio3:2) in the presence of 4.8 g of powdered sodium hydroxide.Recrystallisation from hexane yields a product with a melting point of160°-196° C. M_(n) : 2380, chlorine content: 3.3%.

The following dichlorotriazines are reacted with1-(2,2,6,6-tetramethyl-4-piperidyl)-1,4,7-triazaheptane in analogousmanner:

    ______________________________________                                         ##STR30##                                                                                       m.p.                                                                  molar   (crude                                                     R.sup.2'   ratio   product) --M.sub.n                                                                          Working up                                   ______________________________________                                        c   N(CH.sub.3).sub.2                                                                        1:1     121-126°                                                                      1595 dissolve in acetone,                                                          filter                                     d   N(C.sub.4 H.sub.9).sub.2                                                                 1:1     92-96°                                                                        1790 dissolve in hexane,                                                           filter                                     e   OCH.sub.3  3:2     >260   3170 dissolve in                                                                   methylene                                                                     chloride, filter                           ______________________________________                                    

EXAMPLE 8

The following polyamines are obtained in a manner analogous to thatdescribed in Example 1:

(a) 1,9-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,5,9-triazanonane (boilingpoint 183° C./0.5 mm Hg) from triacetone amine and dipropylene triamine;

(b) 1,9-bis(2,2,6,6-tetramethyl-4-piperidyl)-5-methyl-1,5,9-triazanonane(boiling point 200° C./0.5 mm Hg) from triacetone amine andbis-(3-aminopropyl)-methylamine;

(c)1,17-bis-(2,2,6,6-tetramethyl-4-piperidyl)-1,5,9,13,17-pentaazaheptadecane(boiling point 200° C./0.001 mm Hg) from triacetone amine andtetrapropylene pentamine;

(d)1,13-bis-(2,2,6,6-tetramethyl-4-piperidyl)-1,5,9,13-tetraazatridecane(boiling point 176° C./0.005 mm Hg) from triacetone amine andtripropylene tetramine;

(e)1,14-bis-(2,2,6,6-tetramethyl-4-piperidyl)-1,14-diaza-5,10-dioxatetradecane(boiling point 173° C./0.001 mm Hg) from triacetone amine and4,9-dioxadecane-1,12-diamine, in the presence of 78 g of 5% platinum oncarbon;

(f)1,9-bis(2,2,6,6-tetramethyl-4-piperidyl)-5-cyclohexyl-1,5,9-triazanonanefrom triacetoneamine and bis(3-aminopropyl)-cyclohexylamine;

(g)1,9-bis(2,2,6,6-tetramethyl-4-piperidyl)-5-n-butyl-1,5,9-triazanonanefrom triacetoneamine and bis(3-aminopropyl)-butylamine;

(h)1,9-bis(2,2,6,6-tetramethyl-4-piperidyl)-5-octadecyl-1,5,9-triazanonanefrom triacetoneamine and bis(3-aminopropyl)-octadecylamine;

(i)1,9-bis(2,2,6,6-tetramethyl-4-piperidyl)-5-cyclododecyl-1,5,9-triazanonanefrom triacetoneamine and bis(3-aminopropyl)-cyclododecylamine;

(k) 1,9-bis(2,2,6,6-tetramethyl-4-piperidyl)-5-benzyl-1,5,9-triazanonanefrom triacetoneamine and bis(3-aminopropyl)-benzylamine;

(l) 1,9-bis(2,2,6,6-tetramethyl-4-piperidyl)-5-phenyl-1,5,9-triazanonanefrom triacetoneamine and bis(3-aminopropyl)-aniline;

(m) 1,9-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,9-diaza-5-oxa-nonane(b.p. 154° C./0.05 mm Hg) from triacetoneamine and bis(3-aminopropyl)ether;

(n) 1,9-bis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,9-diaza-5-oxa-nonanefrom 1-methyl-triacetoneamine and bis(3-aminopropyl) ether;

(o) 1-isopropyl-7(2,2,6,6-tetramethyl-4-piperidyl)-1,4,7-triazaheptane(boiling point 115° C./0.05 mm Hg) from1-(2,2,6,6-tetramethyl-4-piperidyl)-1,4,7-triazaheptane and acetone;

(p) 1-isobutyl-7(2,2,6,6-tetramethyl-4-piperidyl)-1,4,7-triazaheptane(boiling point 115° C./0.05 mm Hg) from1-(2,2,6,6-tetramethyl-4-piperidyl)-1,4,7-triazaheptane andisobutyraldehyde;

(q) 1-cyclohexyl-7(2,2,6,6-tetramethyl-4-piperidyl)-1,4,7-triazaheptane(boiling point 151° C./0.05 mm Hg) from1-(2,2,6,6-tetramethyl-4-piperidyl)-1,4,7-triazaheptane andcyclohexanone;

(r) mixture of 1-(1,2,2,6,6-pentamethyl-4-piperidyl)-1,4,7-triazaheptaneand 1,7-bis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,4,7-triazaheptane(boiling point 143°-162° C./0.2 mm Hg) from1,2,2,6,6-pentamethyl-4-piperidone and diethylenetriamine;

(s) 1,7-bis(2,6-diethyl-2,3,6-trimethyl-4-piperidyl)-1,4,7-triazaheptane(b.p. 160° C./0.02 mm Hg) after repeated distillation in a moleculardistillation apparatus) from 2,3,6-trimethyl-2,6-diethyl-4-piperidoneand diethylenetriamine in the presence of 5% (based on the educts) of 5%platinum on carbon;

(t) 1-benzyl-7(2,2,6,6-tetramethyl-4-piperidyl)-1,4,7-triazaheptane(boiling point 172° C./0.4 mm Hg) from1-(2,2,6,6-tetramethyl-4-piperidyl)-1,4,7-triazaheptane andbenzaldehyde.

The above polyamines can be reacted with cyanuric acid derivatives toyield oligomer and polymer compounds by procedures analogous to thosedescribed in Examples 1, 3 or 9.

EXAMPLE 9

(a) With stirring, 46.1 g of cyanuric chloride in 1 liter of toluene areadded dropwise at 0° C. to a solution of 95.4 g of1,7-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,4,7-triazaheptane in 2 litersof toluene. Then 500 ml of 1 N sodium hydroxide solution are added inportions at the same temperature. The mixture is stirred initially for 1hour at 0° C., then for 1 hour at room temperature, and finally for 21/2hours at 40° C. Titration with 0.1 N hydrochloric acid in 2 ml of theaqueous phase reveals 0.042 m-equivalents of base.

The aqueous phase is separated and the toluene solution is washed twicewith water and concentrated in vacuo at a maximum temperature of 40° C.The residue is taken up in chloroform, filtered clear, and concentratedat moderate temperature.

Yield: 100 g of a slightly yellowish product. Melting point: <260° C.;M_(n) : 3150; chlorine content 7.23%. The polymer can be crystallisedfrom hexane as a colourless product. Melting point: 256°-281° C.; M_(n): 4270; chlorine content: 6.98%.

Cyanuric chloride is reacted in the same way with polyamines in themolar ratio 1:1:

    ______________________________________                                                            Product                                                   Polyamine             m.p. (°C.)                                                                        --M.sub.n                                    ______________________________________                                        1    1-cyclohexyl-7(2,2,6,6-                                                                            156-170°                                                                          3200                                          tetramethyl-4-piperidyl)-                                                     1,4,7-triazaheptane                                                      2    1,9-bis(2,2,6,6-tetra-                                                                             112-140°                                                                          3600                                          methyl-4-piperidyl)-1,9-                                                      diaza-5-oxanonane                                                        3    1,7-bis(2,6-diethyl-2,3,6-                                                                         141-186°                                                                          2311                                          trimethyl-4-piperidyl)-1,4,7-                                                 triazaheptane                                                            4    1-isopropyl-7(2,2,6,6-tetra-                                                                       124-143°                                                                          4500                                          methyl-4-piperidyl)-1,4,7-                                                    triazaheptane                                                            5    1,17-bis(2,2,6,6-tetra-                                                                             87-119°                                          methyl-4-piperidyl)-1,5,9,13,17-                                              pentaazaheptadecane                                                      6    5-(2,2,6,6-tetramethyl-4-                                                     piperidyl)-1,5,9-triazanonane                                            7    mixture of 1,7-bis(1,2,2,6,6-                                                                      140°                                              pentamethyl-4-piperidyl)-                                                                          decomp.                                                  1,4,7-triazaheptane (80%) and                                                 1-(1,2,2,6,6-pentamethyl-4-                                                   piperidyl)-1,4,7-triaza-                                                      heptane (20%)                                                            ______________________________________                                    

(b) 30 ml of n-butylamine are added to 10 g of the crude productobtained from cyanuric chloride and1,7-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,4,7-triazaheptane and themixture is refluxed for 16 hours. The solution obtained is diluted with100 ml of methylene chloride, washed three times with 60 ml of 10%sodium carbonate solution, dried over anhydrous sodium sulfate, andconcentrated. The residue is treated with acetonitrile. The insolublesolid is collected by filtration and dried in vacuo, affording 8.2 g ofcolourless product. Melting point: 156°-158° C.; M_(n) : 3800; chlorinecontent: 0.1%. The product is readily soluble in methanol, chloroform,and toluene, soluble in hot hexane, and insoluble in acetonitrile.

The following amines can be reacted in exactly the same manner:

    ______________________________________                                                        Product                                                       Amine             m.p. (°C.)                                                                          --M.sub.n                                      ______________________________________                                        1     cyclopropylamine                                                                              199-209°                                                                            3300                                       2     allylamine      152-156°                                                                            2970                                       3     isobutylamine   151-156°                                                                            4100                                       4     sec-butylamine  169-172°                                                                            3300                                       5     diethylamine    178-183°                                                                            3700                                       6     pyrrolidine     196-203°                                                                            3800                                       7     piperidine      240°  2520                                       8     morpholine      210°  4800                                       ______________________________________                                    

The following products obtained from cyanuric chloride with polyaminesare reacted with butylamine in the same manner:

    ______________________________________                                        Polyamine           m.p. (°C.)                                                                         --M.sub.n                                     ______________________________________                                        9     1,9-bis(2,2,6,6-tetra-                                                                          144-165°                                                                           3300                                            methyl-4-piperidyl)-1,9-                                                      diaza-5-oxanonane                                                       10    1,7-bis(2,6-diethyl-2,3,6-                                                                       99-113°                                                                           2200                                            trimethyl-4-piperidyl)-                                                       1,4,7-triazaheptane                                                     11    1,17-bis(2,2,6,6-tetra-                                                                          98-111°                                                                           4200                                            methyl-4-piperidyl)-                                                          1,5,9,13,17-pentaaza-                                                         heptadecane                                                             ______________________________________                                    

EXAMPLE 10

6 g of the crude polymer obtained in accordance with Example 9(a) fromcyanuric chloride and1,7-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,4,7-triazaheptane are heatedwith 20 ml of 2-ethylhexylamine for 16 hours to 130° C. The reactionmixture is worked up as described in Example 9(b) for the reaction withn-butylamine, affording 5.3 g of a colourless product (m.p. 135°-138°C.; M_(n) : 3600) which is readily soluble in acetone, chloroform andtoluene at room temperature, but is soluble in hexane only at elevatedtemperature.

The following amines are reacted in the same manner:

    ______________________________________                                                          Product                                                     Amine               m.p. (°C.)                                                                         --M.sub.n                                     ______________________________________                                        a     n-hexylamine      136-140°                                                                           2190                                      b     n-octylamine      116-118°                                                                           2300                                      c     n-octydecylamine  99-102°                                                                            2300                                      d     oleylamine        60°  2160                                      e     β-hydroxyethylamine                                                                        220-236°                                                                           2900                                      f     γ-methoxypropylamine                                                                      157-160°                                                                           4500                                      g     cyclohexylamine   186-190°                                                                           2430                                      h     benzylamine       192-193°                                                                           4300                                      i     β-phenylethylamine                                                                         157-162°                                                                           4800                                      k     norbornylamine    236-253°                                                                           2970                                      l     dibutylamine      162-166°                                                                           6000                                      m     2,2,6,6-tetramethyl-4-                                                                          241-256°                                                                           4400                                            piperidylamine                                                          ______________________________________                                    

It is also possible to react the following amines in the same manner:3,5,5-trimethylhexylamine, isotridecylamine, 3-isononyloxypropylamine,3-stearyloxypropylamine, 3,3,5-trimethylcyclohexylamine,cyclododecylamine.

EXAMPLE 11

By a procedure analogous to that described in Example 9(a), cyanuricchloride is reacted with (a)1,9-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,5,9-triazanonane and (b) with1,10-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,4,7-tetraazadecane toproduce polymers which still contain about one chlorine atom in eachtriazine ring.

(a) Melting point: 146°-154° C. M_(n) : 2640

(b) Melting point: 162°-166° C.; M_(n) : 3270.

The further reaction with the N-alkylamines listed in the table belowyields the following products:

    ______________________________________                                                 Polyamine                                                                     1,9-bis(2,2,6,6-                                                                           1,10-bis(2,2,6,6-                                                tetramethyl-4-                                                                             tetramethyl-4-                                                   piperidyl)-1,5,9-                                                                          piperidyl)-1,4,7,10-                                             triazanonane tetraazadecane                                          Amine      m.p. (°C.)                                                                          --M.sub.n                                                                           m.p. (°C.)                                                                      --M.sub.n                              ______________________________________                                        a   n-butylamine                                                                             123-129°                                                                            2590                                                                              142-145°                                                                        5500                                 b   n-hexylamine                                                                             119-122°                                                                            3000                                                                              137-142°                                                                        5200                                 c   n-octylamine                                                                             81-84°                                                                              2210                                                                              114-121°                                                                        5800                                 ______________________________________                                    

EXAMPLE 12

96.4 g of1,14-bis(2,2,6,6-tetramethyl-4-piperidyl-1,14-diaza-5,10-dioxatetradecane,dissolved in 1 liter of toluene, is treated dropwise at 0° C. with 36.8g of cyanuric chloride in 200 ml of toluene. Then 400 ml of 1 N sodiumhydroxide solution are added in portions and the mixture is stirredinitially for 1 hour at 0° C. and then for 4 hours at 40° C. The mixtureis filtered and the aqueous phase separated. The organic phase isconcentrated at a maximum temperature of 90° C. in vacuo and the residueis taken up in methylene chloride. The methylene chloride solution isfiltered and the solvent is removed by evaporation, yielding the productin the form of a soft, tacky resin. M_(n) : 3045.

50 ml of n-butylamine are added to 15 g of the above product and themixture is refluxed for 16 hours. The solution is diluted with methylenechloride, washed twice with dilute sodium carbonate solution and thenwith water, dried, and concentrated, affording as residue a product witha melting point of 66°-92° C. A product with a melting point of 60°-76°C. is obtained by reacting the above product with n-hexylamine.

EXAMPLE 13

In a manner analogous to that described in Example 9, 84.6 g of5-methyl-1,9-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,5,9-triazaheptaneare reacted with 36.8 g of cyanuric chloride to produce a polymer (M_(n): 2900; m.p. 140°-176° C.).

This polymer is reacted with an excess of the following amines asdescribed in Examples 9 and 10:

    ______________________________________                                                        Product                                                       Amine             m.p. (°C.)                                                                          --M.sub.n                                      ______________________________________                                        a     n-butylamine    123-130°                                                                            3000                                       b     n-hexylamine    111-115°                                                                            2400                                       c     n-octylamine    92-97°                                                                              3000                                       c     n-octadecylamine                                                                              62-68°                                                                              2000                                       ______________________________________                                    

EXAMPLE 14

50 g of 2,4-dichloro-6-phenyltriazine, 84.4 g of1,7-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,4,7-triazaheptane, 17.7 g offinely powdered sodium hydroxide and 500 ml of toluene are refluxed for16 hours. The mixture is filtered clear and the filtrate isconcentrated. The residue melts at 136°-151° C.

EXAMPLE 15

6.6 g of the product melting at 60°-76° C. obtained in Example 12 aredissolved in 20 ml of methyl ethyl ketone. To the solution are added 3.5g of finely powdered potassium carbonate and 0.2 g of potassium iodide,followed by the dropwise addition of 3.6 g of benzyl bromide at 80° C.The mixture is refluxed for 40 hours and, after the addition of 50 ml ofmethyl ethyl ketone, filtered. The filtrate is concentrated and theresidue is dissolved in methylene chloride. The solution is washed withwater and the solvent is removed by evaporation. The residue istriturated with acetonitrile and filtered. A benzylation product with amelting point of 73°-86° C. is obtained.

EXAMPLE 16

(a) 20 g of the crude polymer obtained in Example 9(a), 10 ml ofethylenediamine and 50 ml of toluene are refluxed for 16 hours. Themixture is washed with dilute sodium carbonate solution and then withwater, dried over sodium sulfate, and concentrated. The residue istriturated with acetonitrile and filtered, affording a product with amelting point of 203°-206° C.; M_(n) : 4700.

The above procedure is repeated, substituting 20 ml of hydrazine hydrateor 20 g of hexamethylenediamine for ethylenediamine. The physical dataof the resultant products are as follows:

(b) with hydrazine hydrate: m.p. 210° C.; M_(n) : 3800

(c) with hexamethylenediamine: m.p. 181° C.; M_(n) : 4200.

EXAMPLE 17

14.8 g of the crude polymer obtained in Example 9(a) are dissolved in100 ml of toluene and to the solution are added 7 g of dodecylmercaptan,35 ml of 1 N sodium hydroxide solution and 65 ml of water. The mixtureis stirred for 24 hours at room temperature while introducing an excessof triethylamine gas in the course of the first 8 hours. The toluenephase is separated, washed twice with sodium hydroxide and with waterand concentrated. The residue is triturated at -20° C. with acetonitrileand separated, affording a product with a melting point of 66° C.; M_(n): 3010.

EXAMPLE 18

(a) 14.8 g of the polymer obtained in Example 9(a) are suspended in 100ml of n-butanol. Then triethylamine gas is introduced in the course of 6hours and the mixture is allowed for stand for 16 hours. A sodiumn-butanolate solution, prepared from 1 g of sodium and 50 ml ofn-butanol, is then added dropwise. After stirring for 3 hours at roomtemperature, the mixture is concentrated and the residue is taken up inmethylene chloride. The methylene chloride solution is washed withwater, dried over anhydrous sodium sulfate and concentrated. The residueis triturated with acetonitrile, affording a product with a meltingpoint of 179°-181° C.; M_(n) : 5300.

(b) The above reaction is carried out with cyclohexanolate incyclohexanol as solvent. Melting point: 194°-225° C.; M_(n) : 3600.

EXAMPLE 19

(a) 12 g of the product obtained in Example 9(a) are dissolved in 30 mlof toluene and then 2.3 g of acetic anhydride are added to the solution.The mixture is allowed to stand for 2 days at room temperature, thendiluted with toluene, washed with 2 N sodium carbonate solution, driedand concentrated. The residue is treated with acetonitrile, affording 11g of a colourless acetylation product. Melting point: 196°-207° C.;M_(n) : 4300. This product contains about one acetyl group in eachrecurring structural unit.

(b) 11.1 g of undiluted acetic anhydride are boiled for 14 hours with 12g of the starting material of (a). Excess anhydride is removed bydistillation and the residue is worked up as described above. Theresultant product has a melting point of 168°-192° C. and contains about3 acetyl radicals in each recurring structural unit. M_(n) : 4000.

EXAMPLE 20

(a) A solution of 14.8 g of the polymer obtained in Example 9(a) in 100ml of toluene is saturated with trimethylamine gas and allowed to standfor 16 hours. With stirring, a solution of 1.95 g of potassium cyanidein 5 ml of water is added dropwise at room temperature and the mixtureis allowed to react for 3 hours. The toluene phase is separated, washedwith water and evaporated. The residue is triturated with acetonitrileand dried. The product melts at 200°-213° C. M_(n) : 4300.

(b) A solution of 2.15 g of sodium azide in 5 ml of water is reacted inexactly the same way. The polymer azide melts at 181°-214° C. M_(n) :3800.

EXAMPLE 21

(a) 15 g of the polymer obtained in Example 9(a) is dissolved in 50 mlof toluene. With stirring, 6 g of benzoyl chloride and 85 ml of 1 Nsodium hydroxide solution are added to the above solution at 0°-5° C.The mixture is stirred for 14 hours at 0° C., then for 2 days at roomtemperature. The organic phase is separated, washed with 2 N sodiumhydroxide solution and with water, dried and concentrated. The residueis triturated with acetonitrile and filtered. Melting point of theproduct: 198°-210° C.; M_(n) : 4300. The product contains about onebenzoyl group in each recurring structural unit.

(b) The product obtained with n-hexylamine in Example 10 is benzoylatedin the same manner. Melting point of the product: 179°-182° C.

EXAMPLE 22

A mixture of 12.1 g of 2-cyclohexylamino-4,6-dichlorotriazine, 57 g of1,7-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,4,7-triazaheptane, 4.0 g offinely powdered sodium hydroxide and 300 ml of toluene is stirred for 6hours at 40° C. and then refluxed for 14 hours. The insolubleconstituents are removed by filtration and the solvent is distilled off.The product is freed from unreacted starting material in a short waydistillation apparatus. The residue melts at 64°-93° C.; M_(n) : 1000.

EXAMPLE 23

10 g of the polymer obtained in Example 9(a) are dissolved in 90 ml ofchloroform. With stirring, a solution of 3.7 g of cyanuric chloride in10 ml of chloroform and 25 ml of 1 N sodium hydroxide solution are addedat 0°-5° C. The mixture is stirred at 0° C. until 0.02 mole of sodiumhydroxide is consumed. The 5 g of n-butylamine are added and the mixtureis reacted at 40° C. and then at 60° C. for 14 hours. The organic phaseis separated, washed with 2 N sodium hydroxide solution and with water,dried and concentrated. The product still contains one chlorine atom ineach triazine ring. It can be reacted as described in Example 9(b) withamines to produce polymer triaminotriazines.

EXAMPLE 24 Light protective action in polypropylene filaments (130/137)

1000 parts of unstabilised polypropylene (melt index˜15) are mixed in ahigh-speed mixer with 0.5 part of calcium(3,5-di-tert-butyl-4-hydroxybenzyl-monoethyl phosphonate), 1 part ofcalcium stearate and 3 parts of a stabiliser listed in the table below.The mixture is then extruded in an extruder at 220° C. and granulated.The granulate is spun to a 403/37 denier multifilament in a laboratorymelt spinning machine at a maximum temperature of 270° C. and a speed of600 m/minute. This multifilament is stretched and twisted on a drawtwister. The stretch ratio is 1:3.2, such that finally multifilaments of130/37 denier are obtained. These multifilaments are mounted on whitecardboard and exposed in the xenotest 1200. The exposure time up to 50%loss in ultimate tensile strength is the criterion of the protectiveaction. The results are reported in the table.

    ______________________________________                                                           Exposure time up to 50%                                                       loss in ultimate tensile                                   Stabiliser         strength                                                   ______________________________________                                        compound of Ex. 4 (b)                                                                            3500 h                                                     compound of Ex. 4 (g)                                                                            3400 h                                                     compound without stabiliser                                                                       420 h                                                     ______________________________________                                    

What is claimed is:
 1. A polyamine-1,3,5-triazine obtained by thereaction of a halogeno-1,3,5-triazine of formula XVIII ##STR31## whereinR² ' is halogen, cyano, azido, hydrazido, phenyl, --O--R⁷, --SR⁷ or--NR⁸ R⁸ ', in which R⁷ is hydrogen, C₁ -C₁₈ alkyl, C₃ -C₁₂ alkenyl, C₃-C₁₈ alkoxyalkyl, C₃ -C₁₂ cycloalkyl, C₇ -C₁₈ aralkyl, C₆ -C₁₀ aryl orthe radical of the formula II ##STR32## wherein R³ is hydrogen, C₁ -C₁₈alkyl, C₃ -C₁₂ alkenyl, C₃ -C₅ alkynyl, C₃ -C₁₈ alkoxyalkyl, C₂ -C₄hydroxyalkyl which is unsubstituted or substituted by phenyl or phenoxy,or is C₇ -C₁₈ aralkyl, and R⁴ is hydrogen or methyl, and each of R⁸ andR⁸ ' independently is hydrogen, C₁ -C₂₃ alkyl which can be interruptedby oxygen, C₃ -C₁₈ alkenyl, C₃ -C₅ alkynyl, C₂ -C₁₀ hydroxyalkyl, C₂ -C₅cyanoalkyl, C₃ -C₁₂ cycloalkyl, C₇ -C₁₈ aralkyl, C₆ -C₁₀ aryl or theradical of the formula II, or R⁸ and R⁸ ' together with the nitrogenatom to which they are attached form a pyrrolidine ring or a piperidine,morpholine, or hexamethyleneimine ring which is unsubstituted orsubstituted by C₁ -C₄ alkyl, with at least one polyamine of the formula##STR33## wherein X is C₂ -C₆ alkylene, A is --O--, --S-- or --NR--,each R independently is hydrogen, C₁ -C₂₃ alkyl which can be interruptedby oxygen, C₃ -C₁₂ cycloalkyl, C₇ -C₁₈ aralkyl, C₆ -C₁₀ aryl or theradical of the formula II, and c can be an integer from 1 to 4, with theproviso that at least one of R² ' or R is or contains a group of theformula II, and, if desired, treating the compound so obtained with anacylating agent, such that, if a mixture of polyamines of the formulaXIX is used, said mixture can contain an amount of an amine of theformula XIX in which c is 0, and whenever R² " is halogen, or ifterminal halogen atoms are still present, the compound obtained cansubsequently additionally be reacted with compounds of the formula XX

    H--R.sup.2 "                                               (XX)

wherein R² " has the same meaning as R² ' excepting halogen and phenyl.2. The triazine according to claim 1 obtained from reacting cyanuricchloride with at least one polyamine of the formula XIX, wherein X, Aand R are as defined in claim 1 and c can be 1 or 2, such that, if amixture of polyamines is used, said mixture can contain an amount of anamine of the formula XIX in which c is 0, and subsequently reacting theproduct obtained with compounds of the formula XX, wherein R2" is --OR⁷,--SR⁷ or --NR⁸ R⁸ ', and R⁷, R⁸ and R⁸ ' are as defined in claim 1 and,if desired, thereafter acylating the reaction product with an acylatingagent, with the proviso that at least one of R² " or R is or contains agroup of the formula II as defined in claim
 1. 3. The triazine accordingto claim 2, wherein said polyamine is a homogeneous polyamine of theformula XIX, in which c is 1 or 2.